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EP3795653B1 - Matériau synthétique permettant de détecter un rayonnement ultraviolet et/ou un rayonnement x - Google Patents

Matériau synthétique permettant de détecter un rayonnement ultraviolet et/ou un rayonnement x Download PDF

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EP3795653B1
EP3795653B1 EP20200709.2A EP20200709A EP3795653B1 EP 3795653 B1 EP3795653 B1 EP 3795653B1 EP 20200709 A EP20200709 A EP 20200709A EP 3795653 B1 EP3795653 B1 EP 3795653B1
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combination
radiation
group
cations
monoatomic
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EP3795653A1 (fr
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Mika LASTUSAARI
Isabella NORRBO
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University of Turku
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    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
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    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
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    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light
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    • C01—INORGANIC CHEMISTRY
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    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77344—Aluminosilicates
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    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
    • F21K2/00—Non-electric light sources using luminescence; Light sources using electrochemiluminescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
    • G01J1/429—Photometry, e.g. photographic exposure meter using electric radiation detectors applied to measurement of ultraviolet light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/58—Photometry, e.g. photographic exposure meter using luminescence generated by light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/02—Dosimeters
    • G01T1/06—Glass dosimeters using colour change; including plastic dosimeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/16—Measuring radiation intensity
    • G01T1/1606—Measuring radiation intensity with other specified detectors not provided for in the other sub-groups of G01T1/16
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the invention relates to a material, to an ultraviolet radiation sensing material, to an X-radiation sensing material, to a device, to uses of the material, and to a method for determining the intensity of ultraviolet radiation and/or X-radiation.
  • UV irradiation Elevated levels of ultraviolet (UV) irradiation, whether caused by sunlight or tanning ultraviolet devices, has the adverse effect of increasing the probability of skin cancer, other diseases of the skin as well as skin aging. Knowing when to seek for cover from ultraviolet radiation or when to apply or reapply sunscreen lotion is thus of importance.
  • UV ultraviolet
  • UV responsive photochromic organic molecules that change color upon UV exposure can be used.
  • UV indicator bracelets and cards that can be used to indicate the level of solar UV radiation.
  • organic molecules such as spiro-oxazines, spiropyrans, fulgides, fulgimides, bisimidazoles and viologen derivatives.
  • the color from these materials fades when UV exposure is removed, thus making them reusable indicators, but some of them are for single use.
  • many of the reusable photochromic molecules have a short lifetime, and they can thus lose their functionality after too long or too intense UV exposure.
  • Spiro-oxazines may last for two to three years. The drawback for the spiro-oxazines is their high price. The high prices and short lifetimes decrease the usability of these materials in the photochromic UV indicator devices.
  • the inventors have therefore recognized a need for a low-cost ultraviolet radiation sensing material that is stable for a long period of time.
  • the purpose of the invention is to provide a new type of material and its use. Further, the purpose of the invention is to provide an ultraviolet radiation sensing material and its use. Further, the purpose of the invention is to provide an X-radiation sensing material and its use. Further, the purpose of the invention is to provide a device. Further, the purpose of the invention is to provide a method for determining the intensity of ultraviolet radiation and/or X-radiation.
  • the ultraviolet radiation sensing material according to the present invention is characterized by what is presented in claim 13.
  • the X-radiation sensing material according to the present invention is characterized by what is presented in claim 14.
  • the device according to the present invention is characterized by what is presented in claim 15.
  • the method according to the present invention is characterized by what is presented in claim 21.
  • the present invention relates to a material represented by the following formula (I) (M') 8 (M"M′′′) 6 O 24 (X,S) 2 :M ⁇ formula (I) wherein
  • the present invention further relates to a material represented by the following formula (I) (M') 8 (M"M′′′) 6 O 24 (X,S) 2 :M ⁇ formula (I) wherein
  • the present invention further relates to a material represented by the following formula (I) (M') 8 (M"M′′′) 6 O 24 (X,S) 2 :M ⁇ formula (I) wherein
  • the present invention further relates to a material represented by the following formula (I) (M') 8 (M"M′′′) 6 O 24 (X,S) 2 :M ⁇ formula (I) wherein
  • M' represents a monoatomic cation of an alkali metal selected from a group consisting of Na, Li, K, and Rb, or any combination of such cations. In one embodiment, M' represents a monoatomic cation of an alkali metal selected from a group consisting of Li, K, and Rb, or any combination of such cations.
  • M' represents a monoatomic cation of an alkali metal selected from Group 1 of the IUPAC periodic table of the elements, or any combination of such cations; with the proviso that M' does not represent the monoatomic cation of Na alone.
  • the material is a synthetic material. I.e. the material is synthetically prepared.
  • the present invention relates to a synthetic material represented by the following formula (I) (M') 8 (M"M′′′) 6 O 24 (X,S) 2 :M ⁇ formula (I) wherein
  • the present invention relates to a synthetic material represented by the following formula (I) (M') 8 (M"M′′′) 6 O 24 (X,S) 2 :M ⁇ formula (I) wherein
  • the expression “monoatomic ion” should be understood as an ion consisting of a single atom. If an ion contains more than one atom, even if these atoms are of the same element, it is to be understood as a polyatomic ion. Thus, in this specification, unless otherwise stated, the expression “monoatomic cation” should be understood as a cation consisting of a single atom.
  • UV light is electromagnetic radiation with a wavelength from 10 nm (30 PHz) to 400 nm (750 THz).
  • the electromagnetic spectrum of ultraviolet radiation (UVR) can be subdivided into a number of ranges recommended by the ISO standard ISO-21348, including ultraviolet A (UVA), ultraviolet B (UVB), ultraviolet C (UVC).
  • UVA ultraviolet A
  • UVB ultraviolet B
  • UVC ultraviolet C
  • the wavelength of UVA is generally considered to be 315 - 400 nm
  • the wavelength of UVB is generally considered to be 280 - 320
  • UVC is generally considered to be 100 - 290 nm.
  • the ultraviolet radiation comprises ultraviolet A radiation, ultraviolet B radiation and/or ultraviolet C radiation. In one embodiment, the ultraviolet radiation consists of ultraviolet A radiation, ultraviolet B radiation and/or ultraviolet C radiation. In one embodiment, the ultraviolet radiation is ultraviolet A radiation, ultraviolet B radiation and/or ultraviolet C radiation.
  • M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, and wherein the combination comprises at most 66 mole percent (mol-%) of the monoatomic cation of Na. In one embodiment, M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, and wherein the combination comprises at most 50 mol-% of the monoatomic cation of Na.
  • M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, and wherein the combination comprises at most 40 mol-% of the monoatomic cation of Na, or at most 30 mol-% of the monoatomic cation of Na, or at most 20 mol-% of the monoatomic cation of Na.
  • M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, wherein the combination comprises 0 - 98 mol-% of the monoatomic cation of Na. In one embodiment, M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, wherein the combination comprises 0 - 98 mol-%, or 0 - 95 mol-%, or 0 - 90 mol-%, or 0 - 85 mol-%, or 0 - 80 mol-%, or 0 - 70 mol-%, of the monoatomic cation of Na.
  • M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, wherein the combination comprises 0 - 100 mol-% of the monoatomic cation of K. In one embodiment, M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, wherein the combination comprises 0 - 100 mol-% of the monoatomic cation of Rb.
  • M' represents a combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements, wherein the combination comprises 0 - 100 mol-% of the monoatomic cation of Li.
  • M' represents a combination of at least two monoatomic cations of different alkali metals selected from a group consisting of Li, Na, K, and Rb. In one embodiment, M' represents a combination of two monoatomic cations of different alkali metals selected from a group consisting of Li, Na, K, and Rb. In one embodiment, M' represents a combination of three monoatomic cations of different alkali metals selected from a group consisting of Li, Na, K, and Rb. In one embodiment, M' represents a combination of monoatomic cations of Li, Na, K, and Rb.
  • M' represents a combination of a monoatomic cation of Na with a monoatomic cation of Li, a monoatomic cation of K and/or a monoatomic cation of Rb. In one embodiment, M' represents a combination of a monoatomic cation of Na with a monoatomic cation of K or a monoatomic cation of Rb. In one embodiment, M' represents a combination of a monoatomic cation of Na with a monoatomic cation of K and a monoatomic cation of Rb.
  • M' represents a combination of a monoatomic cation of Na and a monoatomic cation of K; or a combination of a monoatomic cation of Na and a monoatomic cation of Rb; or a combination of a monoatomic cation of K and a monoatomic cation of Rb; or a combination of a monoatomic cation of Na, a monoatomic cation of K, and a monoatomic cation of Rb; or a combination of a monoatomic cation of K and a monoatomic cation of Rb.
  • M' represents a combination of a monoatomic cation of Li and a monoatomic cation of Na; or a combination of a monoatomic cation of Li and a monoatomic cation of K; or a combination of a monoatomic cation of Li and a monoatomic cation of Rb; or a combination of a monoatomic cation of Li, a monoatomic cation of K, and a monoatomic cation of Rb; or a combination of a monoatomic cation of Li, a monoatomic cation of Na, a monoatomic cation of K and a monoatomic cation of Rb.
  • M' represents a monoatomic cation of Li. In one embodiment, M' represents a monoatomic cation of K. In one embodiment, M' represents a monoatomic cation of Rb.
  • the combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements has the effect of enabling the preparation of a material that is sensitive to ultraviolet A radiation, ultraviolet B radiation and/or ultraviolet C radiation.
  • the combination has the effect of enabling the preparation of a material being able to indicate the presence of at least one of ultraviolet A radiation, ultraviolet B radiation and ultraviolet C radiation, or the presence of all of ultraviolet A radiation, ultraviolet B radiation and ultraviolet C radiation.
  • M" represents a trivalent monoatomic cation of a metal selected from a group consisting of Al and Ga, or a combination of such cations.
  • M" represents a trivalent monoatomic cation of B.
  • M′′′ represents a monoatomic cation of an element selected from a group consisting of Si and Ge, or a combination of such cations.
  • X represents an anion of an element selected from a group consisting of F, Cl, Br, and I, or any combination of such anions.
  • X represents an anion of an element selected from a group consisting of O, S, Se, and Te, or any combination of such anions.
  • the material is represented by formula (I), wherein M ⁇ is absent. In this embodiment the material is not doped.
  • the material is doped with at least one rare earth metal ion and/or at least one transition metal ion. In one embodiment, the material is doped with at least one rare earth metal ion and at least one transition metal ion. In one embodiment, the material is doped with at least one rare earth metal ion or at least one transition metal ion.
  • the material is represented by formula (I), wherein M ⁇ represents a cation of an element selected from rare earth metals of the IUPAC periodic table of the elements, or from transition metals of the IUPAC periodic table of the elements, or any combination of such cations.
  • M ⁇ represents a cation of an element selected from a group consisting of Eu and Tb, or a combination of such cations. In one embodiment, M ⁇ represents a cation of an element selected from a group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, or any combination of such cations.
  • M' may represent a combination of at least two monoatomic cations of different alkali metals selected from a group consisting of Li, Na, K, and Rb, and wherein the combination is selected in order to provide a predetermined absorption edge for the material.
  • absorption edge should be understood as the energy threshold over which energy the material will change color.
  • the change in the combination of at least two monoatomic cations of different alkali metals selected from Group 1 of the IUPAC periodic table of the elements enables to prepare a material that can be adjusted to detect ultraviolet A radiation, ultraviolet B radiation and/or ultraviolet C radiation.
  • the material is selected from a group consisting of (Na,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Na,Rb) 8g Al 6 Si 6 O 24 (Cl,S) 2 , (Na,K,Rb) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Na,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 :Eu, (Na,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 :Tb, (Li,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Li,Rb) 8 Al 6 Si 6 O 24 (Cl,S) 2 , (Li,K,Rb) 8 Al 6 Si 6 O 24 (Cl,S) 2 , and (Li, Na,K,Rb) 8 Al 6 Si 6 O 24 (Cl,S) 2 .
  • the material is (Na,K) 8 Al 6 Si 6 O 24 (F 0.7 S 0.1 ) 2 . Said material may be used for sensing X-radiation.
  • the material is (Na,K) 8 Al 6 Si 6 O 24 (Cl 0.8 S 0.05 ) 2 . Said material may be used for sensing ultraviolet radiation.
  • the material is synthesized by a reaction according to Norrbo et al. ( Norrbo, I.; Gluchowski, P.; Paturi, P.; Sinkkonen, J.; Lastusaari, M., Persistent Luminescence of Tenebrescent Na8Al6Si6O24 (Cl,S)2: Multifunctional Optical Markers. Inorg. Chem. 2015, 54, 7717-7724 ), which reference is based on Armstrong & Weller ( Armstrong, J.A.; Weller, J.A. Structural Observation of Photochromism. Chem. Commun.
  • the material can be prepared as follows: Zeolite A is first dried at 500 °C for 1 h. The initial mixture is then heated at 850 °C in air for 48 h. The product is then freely cooled down to room temperature and ground. Finally, the product is re-heated at 850 °C for 2 h under a flowing 12 % H 2 + 88 % N 2 atmosphere. The as-prepared materials are washed with water to remove any excess LiCl/NaCl/KCl/RbCl impurities. The purity can be verified with an X-ray powder diffraction measurement.
  • the present invention further relates to an ultraviolet radiation sensing material, wherein the material is a material according to one or more embodiments described in this specification.
  • the present invention further relates to an ultraviolet radiation sensing material, wherein the ultraviolet radiation sensing material comprises the material according to one or more embodiments described in this specification.
  • the present invention further relates to an X-radiation sensing material, wherein the material is a material according to one or more embodiments described in this specification.
  • the present invention further relates to an ultraviolet and X-radiation sensing material, wherein the material is a material according to one or more embodiments described in this specification.
  • the present invention further relates to a device, wherein the device comprises a material according to one or more embodiments described in this specification.
  • the device is an ultraviolet radiation sensor, an ultraviolet radiation detector, or an ultraviolet radiation indicator.
  • the device is an X-radiation sensor, an X-radiation detector, an X-radiation indicator, or an X-radiation dose indicator.
  • the ultraviolet radiation indicator can be applied e.g. in a label on a bottle of skin cream or sunscreen, wherein the change in color would alert the user to the application of the sun protection.
  • the material may be used e.g. on the outside of a window to alert the residents before going out about the ultraviolet radiation intensity.
  • the material can also be mixed as a powder in the raw materials used for the production of a plastic bottle, a sticker, a glass and a similar product that is to be provided with a UV indicator. This offers the products themselves a UV indicator.
  • the products containing the material may also be conceived as jewelry.
  • the material can be used as a display portion of a meter, which is calibrated according to the shade.
  • the present invention further relates to the use of the material according to the present invention for indicating the presence of ultraviolet radiation.
  • the ultraviolet radiation is ultraviolet A radiation, ultraviolet B radiation and/or ultraviolet C radiation.
  • the present invention further relates to the use of the material according to the present invention for indicating the presence of electromagnetic radiation with a wavelength of 0.01 - 400 nm, or of 10 - 400 nm, or of 0.01 - 10 nm.
  • the present invention further relates to the use of the material according to the present invention for indicating the presence of X-radiation.
  • X-radiation is electromagnetic radiation with a wavelength from 0.01 nm to 10 nm.
  • the inventors further surprisingly found out that the synthetic material described in this application, as a result of being subjected to X-radiation, has the technical effect of showing color intensity, which is proportional with the dose of the sensed or detected radiation.
  • a material can be prepared that has the added utility of not changing color in the absence of X-radiation and may thus be used to indicate whether X-radiation is present. The material may thus be used to detect and indicate the amount of X-radiation.
  • the present invention further relates to the use of the material according to the present invention for indicating the presence of ultraviolet radiation and/or X-radiation.
  • the present invention further relates to the use of the material according to the present invention for indicating the presence of ultraviolet radiation and X-radiation.
  • the present invention further relates to the use of the material according to the present invention in a security device.
  • the security device is selected from a group consisting of a thread, a foil and a hologram.
  • the security device is an ink.
  • the security device is used on a banknote, a passport or an identity card.
  • the present invention further relates to a method for determining the intensity of ultraviolet radiation and/or X-radiation, wherein the method comprises:
  • the present invention further relates to a method for determining the intensity of ultraviolet radiation, wherein the method comprises:
  • the present invention further relates to a method for determining the intensity of X-radiation, wherein the method comprises:
  • the present invention further relates to the use of the material according to the present invention
  • step c) comprises visually determining the change in the color of the material.
  • the reference may be e.g. a card or the like that indicates the correlation between the intensity of the ultraviolet radiation and the intensity of the color of the material.
  • the intensity of the color of the material is used to indicate the value of the UV index.
  • a material, a device, a use, or a method, to which the invention is related, may comprise at least one of the embodiments of the invention described hereinbefore.
  • the material has the added utility of being a low-cost material offering stability even in high UV levels as well as decoloration with white light.
  • the material has the added utility that it may not change color in the absence of UV radiation.
  • the material has the added utility that its color can be returned to colorless (white), i.e. decolored, with visible light or heating thus enabling it to be reused.
  • the material has the added utility that it follows well the erythemal action spectrum making it possible to monitor especially UVB and UVC that cause sunburn.
  • the material has the added utility that with sunlight the color intensity can be used to indicate the value of the UV index.
  • the material has the added utility that it may indicate the presence of X-radiation.
  • the material represented by the formula (Na,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 was prepared in the following manner: 0.7000 g of dried (500 °C for 1 h) Zeolite A, 0.0600 g of Na 2 SO 4 and 0.3067 g of KCl powders were mixed together. The mixture was heated at 850 °C in air for 48 h. The product was freely cooled down to room temperature and ground. Finally, the product was re-heated at 850 °C for 2 h under a flowing 12 % H 2 + 88 % N 2 atmosphere.
  • the material represented by the formula (Na,Rb) 8 Al 6 Si 6 O 24 (Cl,S) 2 was prepared in the following manner: 0.7000 g of dried (500 °C for 1 h) Zeolite A, 0.0600 g of Na 2 SO 4 and 0.4957 g of RbCl powders were mixed together. The mixture was heated at 850 °C in air for 48 h. The product was freely cooled down to room temperature and ground. Finally, the product was re-heated at 850 °C for 2 h under a flowing 12 % H 2 + 88 % N 2 atmosphere.
  • the material represented by the formula (Na,K) 8 Al 6 Si 6 O 24 (Cl,S) 2 was prepared in the following manner: 0.7000 g of dried (500 °C for 1 h) Zeolite A, 0.0600 g of Na 2 SO 4 and 0.1800 g of NaCl and 0.0675 g KCl powders were mixed together. The mixture was heated at 850 °C in air for 48 h. The product was freely cooled down to room temperature and ground. Finally, the product was re-heated at 850 °C for 2 h under a flowing 12 % H 2 + 88 % N 2 atmosphere.
  • the material represented by the formula (NaK) 8 Al 6 Si 6 O 24 (Cl,S) 2 :Eu was prepared in the following manner: 0.7000 g of dried (500 °C for 1 h) Zeolite A, 0.0600 g of Na 2 SO 4 and 0.1800 g of NaCl and 0.0675 g of KCl powders were mixed together with 0.002 g of Eu 2 O 3 powder. The mixture was heated at 850 °C in air for 48 h. The product was freely cooled down to room temperature and ground. Finally, the product was re-heated at 850 °C for 2 h under a flowing 12 % H 2 + 88 % N 2 atmosphere.
  • Example 5 Testing of a sample of the materials prepared in example 1, example 2 and example 3
  • a sample of each of the materials prepared in example 1, example 2 and example 4 were tested by irradiating for 1 min with a solar simulator lamp (LOT/QD LS0500) using different irradiances between 300 and 1200 W/m 2 .
  • the irradiances were measured using a hand-held Seaward Solar Survey 100 device.
  • the change in the reflection spectrum of the material was measured with an Avantes AvaSpec 2084x14 spectrometer connected to a 600 micrometer optical fiber.
  • the reflectance measurements were carried out under illumination from a 60 W incandescent light bulb located 20 cm above the sample.
  • Color intensity % of black ⁇ 0.4 * exp UVA lamp power % / ⁇ 25.6 + 10.0
  • Color intensity % of black ⁇ 2.6 * exp UVB lamp power % / ⁇ 446 + 12.7
  • Color intensity % of black ⁇ 2.0 * exp UVC lamp power % / ⁇ 177 + 12.4

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Claims (22)

  1. Matériau représenté par la formule (I) suivante

            (M')8(M"M‴)6O24(X,S)2:Mʺʺ     formule (I)

    dans laquelle
    M' représente une combinaison d'au moins deux cations monoatomiques de différents métaux alcalins sélectionnés dans le groupe 1 du tableau périodique des éléments de l'IUCPA ;
    M" représente un cation monoatomique trivalent d'un élément sélectionné dans le groupe 13 du tableau périodique des éléments de l'IUCPA, ou d'un élément de transition sélectionné dans un groupe quelconque des groupes 3 à 12 du tableau périodique des éléments de l'IUCPA, ou une combinaison quelconque de ces cations ;
    M‴ représente un cation monoatomique d'un élément sélectionné dans le groupe 14 du tableau périodique des éléments de l'IUCPA, ou une combinaison quelconque de ces cations ;
    X représente un anion d'un élément sélectionné dans le groupe 16 du tableau périodique des éléments de l'IUCPA, ou une combinaison quelconque de ces anions, ou X représente un anion d'un élément sélectionné dans un groupe constitué de F, Cl, Br et de I, ou une combinaison quelconque de ces anions ; et
    Mʺʺ représente un cation dopant d'un élément sélectionné parmi des métaux des terres rares du tableau périodique des éléments de l'IUCPA, ou parmi des métaux de transition du tableau périodique des éléments de l'IUCPA, ou une combinaison quelconque de ces cations, ou dans laquelle Mʺʺ est absent.
  2. Matériau selon la revendication 1, dans lequel M' représente une combinaison d'au moins deux cations monoatomiques de différents métaux alcalins sélectionnés dans le groupe 1 du tableau périodique des éléments de l'IUCPA, dans lequel la combinaison comprend de 0 à 98 % en mole, ou de 0 à 95 % en mole, ou de 0 à 90 % en mole, ou de 0 à 85 % en mole, ou de 0 à 80 % en mole, ou de 0 à 70 % en mole du cation monoatomique de Na.
  3. Matériau selon l'une ou l'autre des revendications 1 et 2, dans lequel M' représente une combinaison d'au moins deux cations monoatomiques de différents métaux alcalins sélectionnés dans le groupe 1 du tableau périodique des éléments de l'IUCPA, et dans lequel la combinaison comprend au maximum 66 % en mole du cation monoatomique de Na.
  4. Matériau selon l'une quelconque des revendications 1 à 3, dans lequel M' représente une combinaison d'au moins deux cations monoatomiques de différents métaux alcalins sélectionnés dans un groupe constitué de Li, Na, K et de Rb.
  5. Matériau selon l'une quelconque des revendications 1 à 4, dans lequel M' représente une combinaison d'un cation monoatomique de Na avec un cation monoatomique de Li, avec un cation monoatomique de K et/ou avec un cation monoatomique de Rb.
  6. Matériau selon l'une quelconque des revendications 1 à 5, dans lequel M" représente un cation monoatomique trivalent d'un métal sélectionné dans un groupe constitué d'Al et de Ga, ou une combinaison de ces cations.
  7. Matériau selon l'une quelconque des revendications 1 à 6, dans lequel M" représente un cation monoatomique trivalent de B.
  8. Matériau selon l'une quelconque des revendications 1 à 7, dans lequel M‴ représente un cation monoatomique d'un élément sélectionné dans un groupe constitué de Si et de Ge, ou une combinaison de ces cations.
  9. Matériau selon l'une quelconque des revendications 1 à 8, dans lequel X représente un anion d'un élément sélectionné dans un groupe constitué de O, S, Se et de Te, ou une combinaison quelconque de ces anions.
  10. Matériau selon l'une quelconque des revendications 1 à 9, dans lequel Mʺʺ représente un cation d'un élément sélectionné dans un groupe constitué de Eu et de Tb, ou une combinaison de ces cations.
  11. Matériau selon l'une quelconque des revendications 1 à 10, dans lequel Mʺʺ représente un cation d'un élément sélectionné dans un groupe constitué de Ti, V, Cr, Mn, Fe, Co, Ni, Cu et de Zn, ou une combinaison quelconque de ces cations.
  12. Matériau selon l'une quelconque des revendications 1 à 11, dans lequel le matériau est sélectionné dans un groupe constitué de (Na, K) 8Al6Si6O24 (Cl, S)2, (Na, Rb) 8Al6Si6O24 (Cl, S)2, (Na, K, Rb) 8Al6Si6O24 (Cl, S)2, (Na, K) 8Al6Si6O24 (Cl, S)2:Eu, (Na, K) 8Al6Si6O24 (Cl, S)2:Tb, (Li, K) 8Al6Si6O24 (Cl, S)2, (Li, Rb) 8Al6Si6O24 (Cl, S)2, (Li, K, Rb) 8Al6Si6O24 (Cl, S)2 et de (Li, Na, K, Rb) 8Al6Si6O24 (Cl, S)2.
  13. Matériau de détection de rayonnement ultraviolet, caractérisé en ce que le matériau est un matériau selon l'une quelconque des revendications 1 à 12.
  14. Matériau de détection de rayonnement X, caractérisé en ce que le matériau est un matériau selon l'une quelconque des revendications 1 à 12.
  15. Dispositif, caractérisé en ce que le dispositif comprend un matériau selon l'une quelconque des revendications 1 à 12, la revendication 13, ou la revendication 14.
  16. Dispositif selon la revendication 15, dans lequel le dispositif est un capteur de rayonnement ultraviolet, un détecteur de rayonnement ultraviolet, ou un indicateur de rayonnement ultraviolet.
  17. Utilisation du matériau selon l'une quelconque des revendications 1 à 12 pour indiquer la présence d'un rayonnement ultraviolet.
  18. Utilisation selon la revendication 17, dans laquelle le rayonnement ultraviolet est un rayonnement ultraviolet A, un rayonnement ultraviolet B et/ou un rayonnement ultraviolet C.
  19. Utilisation du matériau selon l'une quelconque des revendications 1 à 12 pour indiquer la présence d'un rayonnement X.
  20. Utilisation du matériau selon l'une quelconque des revendications 1 à 12 dans un dispositif de sécurité.
  21. Procédé de détermination de l'intensité d'un rayonnement ultraviolet et/ou d'un rayonnement X, dans lequel le procédé comprend les étapes consistant à :
    a) utiliser un matériau selon l'une quelconque des revendications 1 à 12, 13 ou 14 ;
    b) soumettre le matériau utilisé à l'étape a) à un rayonnement ultraviolet et/ou à un rayonnement X ;
    c) déterminer un changement de la couleur du matériau provoqué par le rayonnement ultraviolet et/ou le rayonnement X ; et
    d) comparer la couleur du matériau à une référence indiquant la corrélation entre l'intensité du rayonnement ultraviolet et/ou du rayonnement X et la couleur du matériau.
  22. Procédé selon la revendication 21, dans lequel l'étape c) consiste à déterminer visuellement le changement de la couleur du matériau.
EP20200709.2A 2016-05-09 2017-05-08 Matériau synthétique permettant de détecter un rayonnement ultraviolet et/ou un rayonnement x Active EP3795653B1 (fr)

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FI20165392A FI129500B (en) 2016-05-09 2016-05-09 Synthetic material for detecting ultraviolet radiation
PCT/FI2017/050355 WO2017194834A1 (fr) 2016-05-09 2017-05-08 Matériau synthétique pour détecter les rayons ultraviolets et/ou les rayons x
EP17730231.2A EP3469040B1 (fr) 2016-05-09 2017-05-08 Matériau synthétique pour détecter les rayons ultraviolets et/ou les rayons x

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